BTX Fraction Research Articles

Enhancing the selectivity for light olefins through catalytic cracking of n-hexane by phosphorus doping on lanthanum-modified ZSM-5.

Naphtha, as the primary raw material in the production of light olefins, could well accommodate their increasing demand through the energy-efficient process of catalytic cracking with ZSM-5. In the current work, different amounts of lanthanum and phosphorous were loaded on ZSM-5 using the wet impregnation method to tune the acidic properties of ZSM-5 for selective catalytic cracking of n-hexane to produce light olefins. Various characterization techniques such as X-ray diffraction (XRD), Al nuclear magnetic resonance (NMR), temperature-programmed desorption of NH3 (NH3-TPD), Py-Fourier transform infra-red (Py-FTIR), inductively coupled plasma optical emission spectroscopy (ICP-OES), N2 adsorption-desorption, X-ray photoelectron spectra (XPS), and scanning electron microscopy were adopted to investigate the modified zeolites. It was found that adding La to ZSM-5 (0.25wt% to 1wt%) improved the catalytic life and increased the n-hexane conversion (to 99.7%), while the further addition had a negative impact, reducing the conversion rate and deviating the product selectivity towards a substantial, undesired benzene, toluene, and xylene (BTX) fraction (33%). On the other hand, a 64% selectivity for light olefins was achieved on phosphorous-doped ZSM-5 (at a loading amount of 1wt%) while reducing the BTX fraction (2.3%) and converting 69% of the n-hexane. A dual metal-modified ZSM-5 with optimal loading amount, 1P0.25LaZ5 (phosphorus 1wt% and La 0.25wt%), helped boost the light olefin selectivity to 62% in the tuned Lewis acid sites at an n-hexane conversion of about 77% while decreasing the undesired BTX selectivity to 3% by reducing the number of Brønsted sites. Thus, the current study reveals that tuning the acidic sites of ZMS-5 by dual metal augmentation with P.La is an effective way of controlling the amount of undesirable BTX produced at a stable n-hexane conversion rate and substantial olefin selectivity.

In situ Ni2P catalyst for the selective processing of terephthalic acid into BTX fraction

In situ obtained Ni2P-based catalysts were proposed for the selective conversion of terephthalic acid into the benzene-toluene-xylene fraction. The catalysts were characterized by powder X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy and NH3 temperature-programmed desorption. The influence of reaction time, temperature and H2 pressure on the conversion of terephthalic acid and benzene-toluene-xylene selectivity was studied. Direct deoxygenation and decarboxylation were found to be the main reaction pathways using in situ Ni2P catalysts. Selectivity for the benzene-toluene-xylene fraction reached up to 100 % (at full terephthalic acid conversion) under moderate reaction conditions. The reusability of the in situ Ni2P catalyst before and after regeneration was demonstrated.

Tracking the Impact of Koch‐Carbonylated Organics During the Zeolite ZSM‐5 Catalyzed Methanol‐to‐Hydrocarbons Process

AbstractA methanol‐based economy offers an efficient solution to current energy transition challenges, where the zeolite‐catalyzed methanol‐to‐hydrocarbons (MTH) process would be a key enabler in yielding synthetic fuels/chemicals from renewable sources. Despite its original discovery over half a century ago over the zeolite ZSM‐5, the practical application of this process in a CO2‐neutral scenario has faced several obstacles. One prominent challenge has been the intricate mechanistic complexities inherent in the MTH process over the zeolite ZSM‐5, impeding its widespread adoption. This work takes a significant step forward by providing critical insights that bridge the gap in our understanding of the MTH process. It accomplishes this by connecting the (Koch‐carbonylation‐led) direct and dual cycle mechanisms, which operate during the early and steady‐state phases of MTH catalysis, respectively. To unravel these mechanistic intricacies, we have performed catalytic and operando (i.e., UV/Vis coupled with an online mass spectrometer) and solid‐state NMR spectroscopic‐based investigations on the MTH process, involving co‐feeding methanol and acetone (cf. a key Koch‐carbonylated species), including selective isotope‐labeling studies. Our iterative research approach revealed that (Koch−)carbonyl group selectively promotes the side‐chain mechanism within the arene cycle of the dual cycle mechanism, impacting the preferential formation of BTX fraction (i.e., benzene‐toluene‐xylene) primarily.

Tracking the Impact of Koch-Carbonylated Organics During the Zeolite ZSM-5 Catalyzed Methanol-to-Hydrocarbons Process.

A methanol-based economy offers an efficient solution to current energy transition challenges, where the zeolite-catalyzed methanol-to-hydrocarbons (MTH) process would be a key enabler in yielding synthetic fuels/chemicals from renewable sources. Despite its original discovery over half a century ago over the zeolite ZSM-5, the practical application of this process in a CO2 -neutral scenario has faced several obstacles. One prominent challenge has been the intricate mechanistic complexities inherent in the MTH process over the zeolite ZSM-5, impeding its widespread adoption. This work takes a significant step forward by providing critical insights that bridge the gap in our understanding of the MTH process. It accomplishes this by connecting the (Koch-carbonylation-led) direct and dual cycle mechanisms, which operate during the early and steady-state phases of MTH catalysis, respectively. To unravel these mechanistic intricacies, we have performed catalytic and operando (i.e., UV/Vis coupled with an online mass spectrometer) and solid-state NMR spectroscopic-based investigations on the MTH process, involving co-feeding methanol and acetone (cf. a key Koch-carbonylated species), including selective isotope-labeling studies. Our iterative research approach revealed that (Koch-)carbonyl group selectively promotes the side-chain mechanism within the arene cycle of the dual cycle mechanism, impacting the preferential formation of BTX fraction (i.e., benzene-toluene-xylene) primarily.

In Situ Generated Nanosized Sulfide Ni-W Catalysts Based on Zeolite for the Hydrocracking of the Pyrolysis Fuel Oil into the BTX Fraction

The hydrocracking reaction of a pyrolysis fuel oil fraction using in situ generated nano-sized NiWS-sulfide catalysts is studied. The obtained catalysts were defined using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The features of catalytically active phase generation, as well as its structure and morphology were considered. The catalytic reactivity of in situ generated catalysts was evaluated using the hydrocracking reaction of pyrolysis fuel oil to obtain a light fraction to be used as a feedstock for benzene, toluene, and xylene (BTX) production. It was demonstrated that the temperature of 380 °C, pressure of 5 MPa, and catalyst-to-feedstock ratio of 4% provide for a target fraction (IPB −180 °C) yield of 44 wt %, and the BTX yield of reaching 15 wt %.

ZSM-5 zeolites modified with Zn and their effect on the crystal size in the conversion of methanol to light aromatics (MTA)

ZSM-5 zeolite catalysts modified with zinc were prepared by two forms of Zn incorporation the synthesis gel, and ion exchange techniques. The physico-chemical properties of zeolites were studied by XRD, N2-adsorption, NH3 temperature-programmed desorption, 27Al and 29Si MAS NMR, SEM, TEM and TGA. ZSM-5 zeolite in its acid form was exchanged using an aqueous zinc salt solution and demonstrated a significantly higher selectivity for the aromatic products in comparison with the purely acidic catalysts. The samples with distribution of ZnOH+ species are more active than the samples with ZnO sites in the zeolites. The synthesis of zeolite ZSM-5 of nanometric size resulted to present high stability and selectivity towards light aromatics. The influence of the form of zinc incorporation, the acidity and the reaction temperature had a great influence on the catalytic activity. The MTA catalyst lifetime is increased by several times due to the enhanced mesoporosity and decreased acidity. In the present work the zeolite HZSM-5 exchanged with Zn with Si/Al 25 ratio presented conversions close to 100% methanol with 32% selectivity to the BTX fraction, however, this catalyst was deactivated after 8 h of reaction with a weight hourly space velocity of 4.74 h−1 at 450 °C. On the other hand, a HZSM-5 zeolite with nanoscale crystals was found to be more stable in the MTA reaction. The nanometric catalyst showed conversions around 100% methanol after 8 h of reaction and 32.5% selectivity to the BTX fraction to 450 °C. These results clearly indicate that crystal size significantly influence the ZSM-5 lifetime and product distribution.

Sorption and Nanofiltration Characteristics of PIM-1 Material in Polar and Non-Polar Solvents

The affinity of polar extractants (propylene carbonate, dimethylsulfoxide, dimethylformamide, triethylene glycol and dimethylacetamide) and benzene, toluene, p-xylene and m-xylene (so-called BTX fraction) for PIM-1 material was evaluated. The mass-transfer coefficients of selected solvents were determined in organic solvent nanofiltration process. All solvents showed a good affinity toward PIM-1 polymer; while the large values of sorption and PIM-1 swelling degree were in the case of benzene (1.63 g/g, 192%), toluene (1.72 g/g, 186%) and xylenes (1.61–1.76 g/g, 147–170%); while these values for selected polar solvents were in the range of 1.09–1.48 g/g and 83–108%, respectively. The values of sorption and swelling degree were successfully correlated with Hansen’s solubility parameters. Values of permeability coefficients of nonpolar solvents through PIM-1 membranes were 1.5–5.5 times higher than those for polar solvents. With increasing affinity of the solvent toward polymer, the values of the permeability coefficients also increased.

Lewis Acid Catalyzed Conversion of 5-Hydroxymethylfurfural to 1,2,4-Benzenetriol, an Overlooked Biobased Compound.

5-Hydroxymethylfurfural (HMF) is a platform chemical that can be produced from renewable carbohydrate sources. HMF can be converted to 1,2,4-benzenetriol (BTO) which after catalytic hydrodeoxygenation provides a route to cyclohexanone and cyclohexanol. This mixture, known as KA oil, is an important feedstock for polymeric products such as nylons which use benzene as feedstock that is obtained from the BTX fraction produced in oil refineries. Therefore, the conversion of HMF to BTO provides a renewable, alternative route toward products such as nylons. However, BTO is usually considered an undesired byproduct in HMF synthesis and is only obtained in small amounts. Here, we show that Lewis acid catalysts can be utilized for the selective conversion of HMF to BTO in subsuper critical water. Overall, up to 54 mol % yield of BTO was achieved at 89% HMF conversion using ZnCl2. ZnCl2 and similarly effective Zn(OTf)2 and Fe(OTf)2 are known as relatively soft Lewis acids. Other Lewis acid like Hf(OTf)4 and Sc(OTf)3 gave increased selectivity toward levulinic acid (up to 33 mol %) instead of BTO, a well-known HMF derivative typically obtained by acid catalysis. Catalytic hydrodeoxygenation of BTO toward cyclohexanone in water was achieved in up to 45% yield using 5 wt % Pd on Al2O3 combined with AlCl3 or Al(OTf)3 as catalysts. Additionally, a mild selective oxygen induced dimerization pathway of BTO to 2,2′,4,4′,5,5′-hexahydroxybiphenyl (5,5′-BTO dimer) was identified.

Mechanism of deoxygenation in anisole decomposition over single-metal loaded HZSM-5: Experimental study

This work investigates the deoxygenation reaction during the decomposition of anisole (methoxy-rich model compound of lignin) over bi-functional catalyst. The bi-functional catalyst consisted of a single metal loaded on an acid support; the active metals, i.e. Ni, Co, Mo and Cu, were loaded at various rates, and the acid support was HZSM-5 zeolite with a Si/Al ratio of 25 (HZ(25)). Experiments were conducted in a bench-scale fluidised bed reactor within the temperature range from 400 °C to 600 °C. Experimental results revealed that the increase in temperature and metal loading promoted the selectivity of BTX fraction. Nevertheless, a simultaneous increase in the yield of carbonaceous deposits was also observed at the expense of liquid fraction, both phenolics compounds (Phs) and aromatic hydrocarbons (AHs). 500 °C was the preferred temperature for BTX production. Ni-loaded HZ(25) catalyst could dramatically facilitate the conversion of Phs to monoaromatics and increase the selectivity of BTX fraction by 43.4%; Mo-loaded HZ(25) catalyst exhibited the best catalytic activity towards the total production of AHs and promoted the BTX yield by 27.1%. It was also found that 1 wt% was the optimum loading ratio for both Ni and Mo on HZ(25) to obtain the highest BTX yield and selectivity. Characterization of fresh bi-functional catalysts showed that micro polycrystalline metal sites, in the range of 4–10 nm, existed on the fresh catalyst and exhibited strong interaction with the HZ(25) support. For the spent catalysts, large amount of amorphous carbonaceous deposit was observed, ascribed to the polycondensation of aromatic compounds during the reaction. Three reaction pathways were proposed for the catalytic deoxygenation of anisole, with the hydrogen being available in-situ as product of the polycondensation reactions.

Chemical composition of the distillate fractions of coal tar from OAO Altai-Koks

The chemical composition of the distillate fractions with boiling points of to 180, 180–230, and 230–280°C separated from undehydrated coal tar from OAO Altai-Koks was studied by gas chromatography-mass spectrometry. A list of identified aromatic compounds (including N-, O-, and S-containing compounds) and their alkyl derivatives is given. It was found that, upon the complete processing of tar with the recirculation of residual raw materials at the stage of coking and its hydrogenation refining in the presence of suspended Mo- and Ni-containing catalysts and a hydrogen donor (tetralin), the yields of chemical products were the following (wt %): coke, 50–55; absorption oil, 9–12; benzene, naphthalene, tetralin, dimethylnaphthalenes, and other hydrocarbons, 25–30; BTX fraction 4–5; and C1-C4 and CO2, 10–12.

Effect of promotion with cobalt or zinc on the hydrogenating and oligomerizing activities of the Pd/Al2O3 catalyst in the hydrogenation of the BTX fraction

The promoter nature and content effects on the catalytic activity and stability of Pd-Co/δ-Al2O3 and Pd-Zn/δ-Al2O3 bimetallic catalysts in the hydrogenation of dienic and vinyl aromatic hydrocarbons in the BTX fraction have been investigated by IR spectroscopy and temperature-programmed reduction. The Pd : Co (Zn) molar ratio in the catalysts prepared is 1.0 : 0.5, 1.0 : 1.0, or 1.0 : 1.5, and their Pd content is 0.5 wt %. The support is δ-Al2O3 doped with sodium (0.5 wt %). Promotion of the palladium catalyst with zinc and cobalt causes the disappearance of cationic palladium species, thereby reducing the oligomerizing capacity of the active component, and, as was demonstrated by 100-h-long catalytic tests, enhances the stability of the catalyst. The Pd-Co/δ-Al2O3(Na) catalyst with Pd : Co = 1.0 : 1.0 mol/mol is recommended for the hydrogenation of the BTX fraction under industrial conditions. The expected service life of this catalyst between regenerations is 16 months.

Structure-reactivity relationship for aromatics transalkylation and isomerization process with TNU-9, MCM-22 and ZSM-5 zeolites, and their industrial implications

TNU-9 is a medium pore zeolite with a complex tridimensional channel system. Its catalytic properties have been studied in some reactions that involve the BTX fraction, such as benzene and toluene alkylation with methanol, ethanol or isopropanol. These reactions use in practice medium pore zeolites such as ZSM-5 (MFI) or MCM-22 (MWW), and the selectivities obtained with TNU-9 are compared and analyzed from the point of view of the zeolite structure and pore topology, as well as from its possible industrial application. For benzene alkylation to give ethylbenzene (EB), TNU-9 is an active and selective catalyst with selectivities to EB much higher than ZSM-5 and close to those of the industrially relevant MCM-22. However, olefin oligomerization within the pores of TNU-9 occurs in a larger extension than with MCM-22, leading not only to some lower selectivity, but also to a faster catalyst deactivation. In the case of cumene formation, again the selectivity of TNU-9 to the desired product is higher than ZSM-5 but lower than MCM-22, owing to the formation of larger amounts of n-propylbenzene in the former as a result of its pore topology. Nevertheless, TNU-9 may be worth to be studied further for the disproportionation of toluene to give xylenes. In this case, its comparison with ZSM-5 appears of interest. By studying the alkylation of toluene with alcohols of different chain length, i.e. methanol, ethanol and isopropanol, it has been found that TNU-9 has an antagonistic behaviour, closer to ZSM-5 or MCM-22 depending on the activity or selectivity parameters considered that could be explained by its complex topology, formed by 10-ring tortuous channels with crosses as in ZSM-5, and large cavities as in MCM-22.

Separation Benzene and Toluene from BTX using Zeolite 13X

This work deals with the separation of benzene and toluene from a BTX fraction. The separation was carried out using adsorption by molecular sieve zeolite 13X in a fixed bed. The concentration of benzene and toluene in the influent streams was measured using gas chromatography. The effect of flow rate in the range 0.77 – 2.0 cm3/min on the benzene and toluene extraction from BTX fraction was studied. The flow rate increasing decreases the breakthrough and saturation times. The effect of bed height in the range 31.6 – 63.3 cm on benzene and toluene adsorption from BTX fraction was studied. The increase of bed height increasing increases the break point values. The effect of the concentration of benzene in the range 0.0559 – 0.2625g/cm3 and toluene in the range 0.144 – 0.21 g/cm3 was studied. The increasing of inlet solute concentration increases the slope of the breakthrough curve. The amount of toluene adsorbed in the packed bed at any time is higher than that of benzene while it decreases after the saturation time. The best operating conditions in this work for benzene and toluene adsorption are 0.77 cm3/min of feed and 31.6 cm bed height of zeolite 13X.

Effect of acid catalysts on scrap tyre pyrolysis under fast heating conditions

A study has been carried out on the effect of acid catalysts prepared based on HZSM-5, HY and HBeta zeolites on the distribution of volatile products (gas, non-aromatic C 5–C 10 fraction, aromatic C 10 − and tar), in the pyrolysis of tyre material carried out in a fast heating microreactor. The results have been compared with those of thermal pyrolysis. The strategies of using the catalyst in situ and reforming the volatiles generated in thermal pyrolysis have also been compared. The use of a catalyst in situ lowers the pyrolysis temperature by 50 K (to 723 K) and produces a significant increase in the yield of gases and light aromatic C 10 − , at the expense of a decrease in the yield of non-aromatic C 10 − . The yield of tar increases only slightly. The shape selectivity of each zeolite has a significant effect and, consequently, HY zeolite leads to the formation of heavier structures that make up the tar and to aromatic C 10 − , which is favoured by hydrogen transfer capacity. HZSM-5 is more efficient for the formation of gases, although it contributes only to decreasing the molecular weight of aromatic C 10 − fraction. HBeta zeolite catalyst has an intermediate behaviour. Reforming pyrolysis volatiles at 723 K using a HZSM-5 zeolite catalyst efficiently increases (from 2 to 20 wt%) the yield of gases, with a high yield of ethene and propene. The yields of BTX fraction are also very high (around 11.5 wt%).

Screening and optimization of the factors of a detergent admixture preparation

The present research studies the optimization of the preparation of a hydrotrope (mixture of sodium toluenesulfonate and sodium xylenesulfonates) for liquid detergents using experimental designs. The preparation is carried out by selective sulfonation of toluene and xylene present in the BTX fraction of a natural gas. The optimization of five responses has been carried out in two steps. First, we carry out an asymmetrical screening design 2 13 6//18 to select from seven factors, those factors which have significant influence on the amount of residual sodium sulfate in the product and on the total conversion of toluene and xylenes. Secondly, we carry out a Box–Behnken design to optimize three retained factors (temperature, molar ratio of acid to toluene plus xylenes, and the amount of desulfation agent), using response surface methodology. In addition, and in order to reach near-optimal sulfonation conditions, we use the desirability functions to optimize the five responses simultaneously. This allows us to determine for the whole process, sulfonation conditions leading to a high yield of toluene and xylene conversion and acceptable amounts of residual sodium sulfates and sodium benzenesulfonate.

03/02106 Mining of high-methane thin coal seams in the Brzeszcze Coal Mine of the Vistula Coal Company — Practical experience: Malina, Z. and Chojnacki, R. Przeglad Gorniczy, 2002, 58, (9), 1–10. (In Polish)

Direct post-cracking of volatiles from fixed-bed hydropyrolysis of bituminous coal at 580 °C and 1 MPa hydrogen pressure has been studied between 600 and 900 °C at residence times of 0.1 and 1 s. Results showed that post-cracking promotes the formation of gas, mainly methane, at the expense of oil yield. However, the oil composition was richer in benzene, toluene and xylenes (BTX fraction), in naphthalene and methylnaphthalenes, and poorer in phenol, cresols and xylenols (PCX) content. The optimum temperature for post-cracking under conditions investigated was ≈800 °C, but at this temperature the PCX yield was reduced by 40–60%. The PCX formation rate, from heavier phenols, was lower than the PCX dehydroxylation.

Development of a polyfunctional catalyst for benzene production from pyrolysis gasoline

The concurrence of hydrodealkylation, hydrocracking, and hydrodesulfurization reactions necessitates a polyfunctional catalyst in the production of pure benzene from pyrolysis gasoline or other industrial mixtures containing various alkylaromatic and nonaromatic hydrocarbons. A chromium catalyst was developed in this study with comparable performance to the commercial catalyst Pyrotol H-9430 (Houdry, USA). The new catalyst contained 15 wt.% Cr and was doped with KF. When tested utilizing a hydrocleaned BTX fraction of pyrolysis gasoline, it preserved its benzene selectivity and hydrocracking activity for 3000 h, but lost about 10% of its hydrodealkylation activity. The deactivated catalyst completely recovered its original surface properties and hence activity when subjected to oxidative regeneration. The developed catalyst maintained its Cr and KF content in regeneration as it did in drying, calcination, and reaction. The characteristics of the catalyst were examined by BET, XRD, DTA, TGA and electron microscope.

Mixture design applied to the formulation of hydrotropes for liquid detergents

In a previous study, we presented a new method for preparing a mixture of sodium toluenesulfonates (STS), sodium xylenesulfonates (SXS), sodium benzenesulfonate (SBS) and Na 2SO 4 by sulfonating the BTX fraction of a Tunisian natural gas. Such mixtures can be used as a hydrotrope agent for concentrated liquid detergents. In the present work, we performed a mixture design in order to study the effect of each of these four components on the clear point and the viscosity of a liquid detergent, and therefore, to determine the conditions allowing to improve the effectiveness of the hydrotrope. Twenty-eight combinations of the 4 components out of 51 candidate points are selected by the Nemrod-W software according to the D-optimal criterion to fit two polynomial models. The statistical study shows that the fitted models were adequate to describe the clear point and the viscosity responses. Optimal conditions allowing to lower the two responses are then looking for by examining the response surface both as a contour plot, and as three-dimensional surface plot and the response trace. We prove that Na 2SO 4 exhibits a harmful negative effect, while SXS and STS exhibit, respectively, a strong and moderate positive effect on both clear point and viscosity responses. As expected, SBS has a harmful effect on the two responses but the magnitude of this effect is lesser than that predicted by the preliminary experiments carried out with SBS alone. This phenomenon is explained by the formation of heteroassociation between SBS, STS and SXS similar to what is found in surfactants. The effectiveness of the hydrotrope, obtained by sulfonation of the BTX fraction of the Tunisian natural gas, is really improved by removing sulfates either by adding lime to precipitate gypsum, or isopropanol to reduce the solubility of Na 2SO 4.

"Chemometrics" applied to the optimization of the preparation of hydrotopes for detergents starting from BTX fraction of natural gas

Manufacturers of cleaning products use hydrotopes to increase the solubility of surfactants in concentrated liquid detergents. In contrast to benzenesulfonate, alkylbenzenesulfonates with short chains (n < 4) are used as hydrotopes. In this paper, we present the results obtained from the preparation of toluenesulfonic and xylenesulfonic acids by selective sulfonation of toluene and xylenes present in the BTX fraction (benzene, toluene, xylenes) of the Tunisian natural gas MISKAR deposit. Chemometrics were applied to determine the optimal experimental conditions for the selective sulfonation of toluene and xylenes, we use a 2 IV 6-2 fractional factorial design in addition to several analytical methods (GC, HPLC, FTIR...). These conditions were found to be: the use of concentrated sulfuric acid as sulfonating agent, the azeotropic elimination of water during the reaction, a temperature of 110 °C, a duration of 9 hours and a molar ratio of sulfuric acid to toluene plus xylenes of 0.8. The application of all of these experimental conditions gives an aqueous phase with a composition that can be used very effectively as hydrotope agent in liquid detergents. This conclusion was the outcome from comparing the effect of our product on the clear point of a typical premium formulation of a liquid detergent to that of sodium xylenesulfonates, the most important hydrotope for light duty liquids.

Hindcasting volatile chemical emissions to air from ponded recycle oil

AbstractBecause of weathering, while abandoned for over a decade, the floating oil at the site of a former oil recycling operation became depleted of numerous volatile and semi‐volatile constituents. The chemical record preserved in the bottom sediment provided the key information from which operating conditions over the period 1973–1982 could be reconstructed. Chemical concentrations in the oil could be determined and coupled with an environmental chemodynamic model to quantifying chemical release rates to air. The oil contained elevated levels of naphthalene. The oil, BTX fraction, several chlorinated solvents, and two PCB Aroclors were modeled. Annual average emission rates were 4000 kg for naphthalene, 840 for TCE, 300 for benzene and 14 for A‐1248. Fundamental results obtained are: a) the criteria required for using historic, bed‐sediment data to reconstruct key chemical processing information at a former plant site and b) field data on volatile and semi‐volatile chemical emission kinetics from deep, floating oil pools.